Azo dyestuffs



Patented Nov. 1 6, 1937 PATENT OFFICE Azo DYESTUFFS Max Lange, Frankfort-on-the-Main-Hochst, Germany, assignor to General Aniline Works, 'Inc.,

New York, N. Y., a corporation of Delaware No Drawing. Application July 9, I 1935, Serial No. 30,563. In Germany August 4, 1934 4 Claims. (01. 260-92) The present invention relates to azo-dyestufis;

more particularly it relates to azo-dyestufis of the following general formula:

N=N-Z 10 som wherein R. represents one of the groups OH,

. O-alkyl, O-aryl, O-aralkyl or the grouping in which X and Y stand for hydrogen, alkyl,

2 aryl or aralkyl radicals, R. and R stand for hya drogen, alkyl, aryl or aralkyl radicals and Z means the; radical of an aminonaphtholsulfonic acid orwherein R represents one of the groups OH,

O-alkyl, O-aryl, O-aralkyl or the grouping in which X and Y stand for hydrogen, alkyl, aryl 6& or aralkyl radicals, and wherein R. and R." stand I have found that these valuable azo-dyestufi for hydrogen, alkyl, aryl or aralkyl radicals, with an aminonaphtholsulfonic acid or a derivative of a 1-aryl-5-pyrazolone containing at least one group lending solubility.

The dyestuffs-thus obtained are particularly 5 suitable for dyeing animal fibers; they have a good levelling power and yield dyeings of good fastness properties, particularly of a very good fastnes's to light'and a good fastness to perspiration.- A's-far as the dyestuffs are capable of being 10 after-chromed, dyeings of good fastness to potting and to fulling are obtained.

,The .:new dyestufis have the same good fastnessproperties as those of German Patent 544,815, and, moreover, have a better levelling power. The dyestufis of thepresent invention have also a better levelling power and a better fastness to light than the dyestufis of German Patents 476,079 and 595,680.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto; the parts are by weight, unless otherwise stated. 2

(1) 16.4 parts of the base of the following conare introduced, while stirring, into 50 parts of sulfuric acid of 50 per cent. strength and con verted into the diazo-compound by causing about 86 parts ofa solution of per cent. strength of sodium nitrite to run into the mixture at a temperature of about 0 C. The strongly acid diazo-solution thus obtained is neutralized with a solution of about 32 parts of sodium bicar- 4.0 bonate' in about 300 parts of water and, if necessary; filtered. A neutral, aqueous solution, prepared in the usual manner of 12.5 parts of 2- amino-8 naphthol-6-sulfonic acid, is introduced into this diazo-solution at about 0 C.-5 C. After some time about 20 parts of crystallized sodium acetate are added, until the mass no longer has an acid reaction to Congo paper; the whole is heated to about 70 C. and the dyestufi is salted out with about 100 parts of sodium chloride, then filtered at about 40 C., pressed and dried. It dyes wool in an acid bath vivid bluish red tints. The dyeing thus obtained has a very good fastness to light and a good fastness to perspiration. The dyeings on unloaded silk and on loaded silk are also very fast to light. The dyestuff corresponds with the following formula:

HOaS

bonate solution. When coupling is. completed the reaction mixture is heated to about 70 (L, mixed with about 200 parts of sodium chloride and rendered feebly acid to Congo paper by addition. of hydrochloric acid. After cooling, the dyestufi is isolated in the usual, manner and dried. It dyes wool in an acid bath clear yellow tints of, very good fastness. to light and good fastness to perspiration.

(3) 16.4. parts of the base referred toin Ex.- ample 1 are diazotized as described in. 171185136X."- ample and the diazo-compound. is. coupledv with a solution of about 15.2 parts of 1-(2'-chloro-5'- sulfo)-phenyl-3:-methyl-B-pyrazolone in an ex.- cess of sodium carbonate solution. A dyestufi' is obtained which dyeswool in an. acid bath a yellow tint of a somewhat more greenish hue than that described in Example 2. The dyeing possesses the same good properties (4) 13.6 parts of the base of the following constitution:

are introduced, while stirring, into a mixture of 15 parts by volume of hydrochloric acid of 30 per cent. strength and 25 parts of water and diazotized at about C. with about 8.6 parts of a solution of sodium nitrite of 40 per cent. strength. A solution of 12.5 parts of 2-amino-8- naphthol-6- sulfonic acid. neutralized, with sodium: carbonate is introduced atabout 0 G. into this diazo-solution; the whole isneutralized. with,

about 15 parts of crystallized sodium acetate, heated to about 60 C. after coupling is completed and gradually mixed with about 200 parts by volume of a saturated solution of sodium chloride; the mixture is allowed to cool and. the dyestuif is isolated in the usual manner. It dyes wool in an acid bath a tint which is about the same as that, of the dyestufi obtained according to Example 1 and possesses similar properties.

(5) 14.3 parts of the compound of the following constitution:

NHz

are gradually introduced into a mixture of 25 parts by volume of hydrochloric acid of 30 per cent. strength and 25 parts of water; at the same time about 8.6 parts of a solution of 40 per cent strength of sodium nitrite are run in at about C. to about 20 C. A neutral solution prepared in the usual manner from 12.5 parts of 2-amino-8-naphthol-6-sulfonic acid and sodium carbonate is run into the diazo-sol'ution after the latter has been diluted with a little ice-water and, if necessary, filtered; the mixture is neutralized with about 30 parts of crystallized sodium: acetate and, as soon as the coupling is completed, it is heated to about 60 C. about 70 C. Then the mass is rendered feebly alkaline by addition of about 14 parts of calcined sodium carbonate and the dyestuff is filtered at about 40 C. It. dyeswool in an acid bath a red tint of a much bluer hue than that of the dyestuff obtained according to Example 1. The dyeing has a good fastness to light and to perspiration.

(6*) The diazo-solution prepared from 14.3 parts. of the base referred to. in Example. 5 is run at about 0 C. into a solution of 19' parts of lacetamino- 8 -hydroxynaphthalene-3.6-disulfonic acid in 100 parts of water and 250 parts by volume of a 2N-sodium carbonate solution. When the coupling is complete the whole is heated to about 60 C. to about 70 C. and the dyestuff is salted out by means of sodium chloride and filtered at about 30 C. It dyes wool in an acid bath a yellowish red tint of good fastness to light and to perspiration.

(7) 14.3 parts of the base referred to in EX- ample 5 are d-iazotized as described in that ex-- ample. The clear diazo-solution is run at about 0 C. to about 5 C. into a solution of 16.5 parts of 1- (2'-hydroxy-3'-carboxy-5'-sulfo) -phenyl-3- methyl-S-pyrazolone in an excess of sodium carbonate solution and the dyestuff is isolated in the usual manner by addition of sodium, chloride. It dyes wool in. an acid bath a vivid reddish yellow tint of a very good fastness to light. and a good fastness to perspiration and to sea-water.

By after-chroming a. reddish yellow'tint of very good fastness; toperspiration, to sea-water, to: potting andto fulling. is obtained.

8 1.4.3. parts of the base referred. to in. Example 5 are diazotized and the. diazo-compound is coupled with 15.2 partsv of 1-(2'-chloro-5- sulfo)-phenyl-3-methyl-5-pyrazolone in a solution rendered alkaline by means of sodium carbonate. The dyestuif thus obtained dyes wool in an acid bath greenish yellow tints which have the same advantageous properties of fastness as the dyestufi obtainable according to Example '7.

(9) 13.6 parts of the compound of the following constitution:

OOOH

S O2N(C2H5)2 are dissolved in 100 parts of water and 4.5 parts by volumeoicaustic soda solution of 40 B. The solution thus prepared is allowed' to run into a mixture of 50 parts of wateriand 12.5 parts by volume :ozf hydrochloric acid: of 37 per cent strength and diazotized at 0 C. with about 50 parts by volume of a normal solution of sodium nitrite. The magma of the diazo-compound thus obtained is coupled in known manner with a solution, rendered alkaline by means of sodium carbonatemf 15.2 parts of gl-(2 -chloro-5-sulfo) phenyl-3-methyl 5 -.pyraz olo ne. The dyestuff dyes wool in an acid bath a greenish-yellowtint of good fastness to light and to perspiration. By after-chroming a more reddish yellow of good fastness to washing and to fulling is obtained.

The following table shows a further number of azo-dyestuifs which may be obtained according to the present invention:

wherein R represents-a. member of the group consisting of OH, O-alkyl and the grouping in which X and Y stand for members of the group consisting of hydrogen, alkyl and phenyl radicals, R, and R ,stand for members of the group consisting of hydrogen, alkyl and phenyl radicals and Z means the radical of an aminonaphtholsulfonic acid, dyeing the animal fiber in general red shades of good fastness properties, particularly of a very good fastness to light and a good fastness to perspiration.

Diazo components 1 aminobenzene 2 carboxylic acid-5-sulionic acid-amide.

' 1 aminobenzene 2 carboxylic acid-fi-sulionic acid-amide.

1 eminobenzene 2 carboxylic aeid-5-sulionlc acid-amide.

1 aminobenzene 2 carboxylic acid-fi-sulfonic acid-phenylamide.

1 aminobenzene 2 carboxylic acid-5-su1i0nic acid-phenylamide.

1 aminobenzene 2 carboxylic acid-fi-sulfonic acid-phenylamide.

l aminobenzene 2 carboxylic acid-5-sulionic acid-diethylamide.

1 aminobenzene 2 carboxylic acid-fi-sulfonic acid-N-ethylphenylamide.

1 aminobenzene 2 carboxylic acid-5-sulfonic acid-Nethylphenylamide.

1 aminobcnzene 2 carboxylic acid-5-sulfonic acid-N-ethylphenylamide.

1 aminobenzene 2 carboxylic acid amide 5 -sulfonic acid amide.

l aminobenzene 2 carboxyhc acid-amide-5-sulfonic acidamide.

1 aminobenzene 2 carboxylic acid-methylamide 5 sulionic acid-methylamide.

1 aminobenzene 2 carboxylic acid ethylamide 5 sulionic acid-ethylamide.

1 aminobenzene 2 carboxyhc acid ethylamide 5 sulionic acid-ethylamide.

1 aminobenzene 2 carboxylic acid cliethylamide 5 sulionic acid-diethylamide.

1 aminobenzene 2 carboxylic acid N-ethylphenylamide-5 sulfonic acid-N-ethylphenylamide.

1 aminobenzene 2 carboxyhc acid-N-ethylphenylamide-E- sulfonic acid-N-ethylphenylamide.

Coupling components Tints l acetylamino 8 hydroxy Red.

na 1()1hthalene-3.6-disulfonic aci 2-amino-8-hydroxynaphtha- B In is h lene-6sul ionic acid (in an red. acid medium).

"3-methyl-5-pyrazolone.

1- (2-hydroxy-3-earboxy-5- Yellow.

sulfophenyl) -3-m'ethyl- 5- pyrazolone.

2-amino-8-hydroxynaphtha- B 1 u i s h lene-fi-sulfonic acid (in an red. acid medium).

2- phenylamino- 8- hydroxy Brown.

naphthalene-fi-sulfonic acid.

2-amino-8-hydroxy-naphtha- Red.

lene-G-sulfonic acid.

1- (2-chloro-5'-suliophenyl)- Yellow.

3-methyl-5-pyrazolone.

2-amino-8-hydroxynaphtha- B l u i s h lene-6-sulion1c acid (in an red. acid medium).

1-(4-suli'ophenyl)-3-methyl- Reddish fi-pyrazolone. yellow.

Z-amino-S-hydroxy-naphtha- B In is h lene-fi-sulionic acid (in an red. acid medium).

l-(2-hydroxy-3-carboxy-5- Yellow.

sul fophenyl) -3 -methyl- 5- pyrazolone.

2-amino-8-hydroxy-naphtha- B In is h lene-fi-sulionic acid (in an red. acid medium 1 (2 chloro 5' sulio- Yellow.

phenyl) 3 methyl 5 pyrazolone.

2 amino 8 hydroxynaph- B in i s h thalene-fi-sulfonic acid (in red. an acid medium).

1 (4' sulfophenyl) 3 car- Yellow.

boxylic acid-ethylester-fipyrazolone.

1 (2"- hydroxy -3 carboxy- Yellow.

5-sulfopheny1)-3-methylfi-pyrazolone.

2 amino 8 hydroxynaph Red.

thalene-d-sulfonic acid (in an acid medium).

Iclaim: 1. The azo-dyestufl's of the following general formula;

SOr-N \RII 2. The azo-dyestufl? of the following formula:

3', -'Ihe azu-dyestufi: of vthe; fol iqwing formula: 4. The: azo-dyesfiufi of the foil owing formula:

NH: O O O CH:

SOaH

SOz.N(CaHa)2 B:Og.N%(CS-Hs)z V dyeing wool in an acid bath vivid bluish-red 10 dyeing wool in acid bath vivid bluish-red shades of very good fastness to light and good shades of good fastness to light and to perspirafastness to perspiration. tion. 7 MAX LANGE. 

